JPH055350B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to novel squaraine compounds and the incorporation of these compounds into photoresponsive devices having layered structures. In one embodiment of the present invention, novel fluorobenzylaminosquaraine compounds are provided. The compounds are useful as organic photoconductive materials in photoresponsive devices having layered structures, particularly devices containing amine hole transport layers. As described above, the present invention provides a photoresponsive device containing a novel fluorobenzylaminosquaraine compound as a photoconductive layer. The sensitivity of these photoresponsive devices can be altered or enhanced, making these devices responsive to visible light and to infrared light required for laser printing. . Accordingly, the fluorobenzylaminosquaraine-containing photoresponsive devices of the present invention function to enhance or reduce the inherent properties of the incorporated charge carrier photogenerating material in the infrared and/or visible region of the spectrum. The device can be made responsive to visible and/or infrared wavelengths of light.

A number of different electrophotographic photoconductive members are known, including devices having a uniform layer of a single material, such as fused selenium, or a composite laminate structure containing a dispersion of photoconductive material. An example of a type of composite electrophotographic photoconductive member is described, for example, in US Pat. No. 3,121,006. This patent discloses fine particles of a photoconductive inorganic compound dispersed in an electrically insulating organic resin binder. These components include, for example, a binder layer applied to a paper support and containing uniformly dispersed particles of zinc oxide. The binder materials disclosed in this patent include materials such as polycarbonate resins, polyester resins, and polyamide resins, which ring the injected charge carriers generated by the photoconductive particles by a significant distance. cannot be sent. Therefore,
As a result, the photoconductive particles must be in substantial particle-to-particle contact throughout the layer for the purpose of allowing the dissipation of charge necessary for cyclic operation. In order to obtain sufficient photoconductive particle-to-particle contact for such rapid discharge,
Along with the uniform dispersion of photoconductive particles mentioned here,
A relatively high volume concentration of photoconductive material i.e. approximately 50
% by volume is generally required. Such high photoconductive loading can result in a breakdown of the physical continuity of the resin binder, thereby significantly reducing its mechanical properties.

Photoreceptive materials composed of inorganic or organic materials are also known, in which the charge carrier generation and charge carrier transport functions are achieved by means of discontinuous contact layers. Furthermore, photoreceptive materials having a layered structure are disclosed in the prior art, which materials include a protective film layer of an electrically insulating polymer. However, as electrophotographic technology continues to advance, copiers are required to meet ever more demanding requirements in order to achieve greater performance levels and higher quality images. It would also be desirable to have a photoresponsive device with a layered structure responsive to visible and/or infrared light selected for use in laser printing devices.

Other stacked photoresponsive devices have recently been announced. These devices are overcoated with a separate generation layer and a hole injection layer overcoated with the transport and hole transport layers described in U.S. Pat. No. 4,265,990 and further overcoated with a photogeneration layer. It consists of a photoresponsive material and a protective coating of insulating organic resin. See US Pat. No. 4,251,612. Examples of photogenerating layers disclosed in these patents include trigonal selenium and phthalocyanines, and examples of transport layers include certain diamines described herein. See US Pat. Nos. 4,265,990 and 4,251,612 on these points.

Numerous other patents describe photoresponsive devices with stacked devices containing emitting substances. For example, US Pat. No. 3,041,167 discloses an overcoated image element having an electrically conductive support, a photoconductive layer, and an overcoat layer consisting of an electrically insulating polymeric material. The element may, for example, be electrostatically charged such that the element is first charged with an electrostatic charge of a first polarity and imagewise exposed to form an electrostatic latent image which is then developed to form a visible image. Used in photocopy machines. The image element can be charged with an electrostatic charge of a second polarity opposite the first polarity before the next image cycle. This second polarity charge is applied sufficiently across the element to ultimately create a second polarity electric field. At the same time, a mobile charge having a first polarity is created in the photoconductive layer, for example by applying a voltage to the conductive support. An image potential is present throughout the photoconductive layer and overcoat layer that upon development forms a visible image.

Also, Belgian Patent No. 763,540 discloses an electrophotographic element having at least two electrically active layers. This first photoconductive layer can photogenerate charge carriers that can be injected into the continuous active layer containing the organic transport material. This organic transport material has virtually no absorption in the spectral region for which it is intended to be used, but is capable of injecting holes generated by light from the photoconductive layer, and It can be circulated through this active layer. Further, U.S. Pat. No. 3,041,116 discloses a photoconductive material comprising a transparent plastic material overcoated onto a layer of fused selenium carried on a support.

Further, U.S. Nos. 4,232,102 and 4,233,383 disclose photoresponsive images containing trigonal selenium doped with sodium carbonate, sodium selenite, and trigonal selenium doped with barium carbonate and barium selenite or mixtures thereof. elements are disclosed. Additionally, U.S. Patent No.
No. 3,824,099 discloses certain photosensitive hydroxysquaraine compounds. The squaraine compounds disclosed in this patent are photosensitive in conventional electrostatographic imaging equipment.

Pending applications also disclose the use of known squaraine compounds, such as hydroxysquaraine, as photoconductive layers in infrared-sensitive photoresponsive devices. More specifically, this pending application includes a support, a hole blocking layer, an optional adhesive interface layer, an inorganic photogenerating layer, and a squaraine compound selected from a variety of squaraine compounds, including hydroxysquaraine compounds. An improved photoresponsive device is disclosed that includes a hole transporting layer and a photoconductive compound that can enhance or reduce the inherent properties of a photogenerating layer. ing.

Additionally, pending applications describe novel julolidingl squaraine compounds, such as bis-9-(8-hydroxydiulolidinyl) squaraine, which are photosensitive to infrared and/or visible light. Disclosed is use as a photoconductive material in responsive devices. As shown in this pending application, one embodiment of this improved photoresponsive device includes a support, a hole blocking layer, an optional adhesive interface layer, an inorganic photogenerating layer, and and a hole transport layer. Regarding these points, "Photoresponsive device with novel squaraine compound"
See pending US Pat. No. 493,114/83 entitled.

Although squaraine compounds are known, there continues to be a need for new squaraine compounds, particularly squaraine compounds with excellent photosensitivity. Additionally, there continues to be a need for photoresponsive devices that include new highly photosensitized squaraine compounds as photoconductive layers. Additionally, when used in a laminated photoresponsive imaging device, it can form acceptable images and the device can be used repeatedly for many imaging cycles without degrading due to the environment or ambient conditions of the device. There continues to be a need for new squaraine compounds that can Additionally, there continues to be a need for improved layered imaging elements in which the squaraine compound selected as one of the layers is substantially non-toxic to the user of the device. It is also sensitive to a broader range of wavelengths, and more specifically to infrared and visible light, and thus can be used in a number of imaging and printing devices. There continues to be a need for coated photoresponsive devices.

It is therefore an object of the present invention to provide new fluorobenzylaminosquaraine compounds.

Another object of this invention is to provide improved photoresponsive imaging elements containing novel fluorobenzylaminosquaraine compounds.

Yet another object of the invention is to provide an improved photoresponsive device that is panchromatic and therefore sensitive to visible as well as infrared light.

It is a more specific object of the present invention to provide an improved overcoated photoresponsive device that includes a photoconductive layer and a hole transport layer having a novel squaraine photosensitive dye.

Yet another object of the invention is to provide an improved overcoated photoresponsive device comprising a hole transporting layer and a photoconductive layer comprising a novel fluorobenzylaminosquaraine compound coated thereon. It is to provide.

Yet another object of the present invention is to provide a photoresponsive device comprising a photoconductive compound comprising a novel fluorobenzylaminosquaraine compound disposed between a hole transporting layer and a photogenerating layer. .

Yet another object of the present invention is to provide an improved laminate photoresponsive device comprising a novel squaraine photoconductive compound disposed between a photogenerating layer and a support.

Yet another object of the invention is an improved overcoated photoconductive layer comprising a photogenerating compound disposed between a hole transporting layer and a photoconductive layer comprising a novel fluorobenzylaminosquaraine compound. An object of the present invention is to provide a response device that is responsive to infrared light and visible light.

Another object of the present invention is to provide an improved photoconductive layer comprising a novel squaraine compound disclosed herein disposed between a hole transporting layer and a layer comprising a photogenerating compound. An object of the present invention is to provide an overcoated photoresponsive device that is responsive to infrared and visible light.

Yet another object of the present invention is to provide methods of imaging and printing using the improved overcoated photoresponsive devices described herein.

These and other objects of the present invention are directed to () bis(2-fluoro-4-methylbenzylaminophenyl)squaraine, () bis(2
-Fluoro-4-methyl-p-chlorobenzylaminophenyl)squaraine, ()bis(2
A novel fluorobenzyl squarine selected from the group consisting of -fluoro-4-methyl-para-fluorobenzylaminophenyl)squaraine and ()bis(2-fluoro-4-methyl-methchlorobenzylaminophenyl)squaraine. This is accomplished by providing a line compound. These squaraine compounds are represented by the following formula.

The novel squaraine compounds disclosed herein generally contain a suitable fluoroaniline derivative, such as meta-fluoro-N-methyl-N-benzylaniline, and squaric acid in a ratio of about 4 to about 1, preferably about 1.5 to 2.5. in the presence of an aliphatic alcohol and an optional azeotropic cosolvent in a molar ratio of . Approximately 400 ml of alcohol is used per 0.1 mol of squaric acid, but up to 1000 ml of alcohol per 0.1 mol of squaric acid can be selected. This reaction is generally around 75
C. to about 130.degree. C., preferably 95.degree. C. to 105.degree. C., with stirring until the reaction is complete. The desired product is then separated from the reaction mixture by known methods, such as filtration, and this product is
Identification is done using analytical instruments such as NMR and mass spectrometry. Elemental analysis of carbon, hydrogen, fluorine, nitrogen and oxygen is chosen to further aid in the identification of the products obtained.

This fluoroaniline derivative can be prepared by a number of methods. reacting a known fluoroaniline, such as metafluoroaniline, with a tolualkyl orthoformate, including trimethyl orthoformate, in a molar ratio of about 1 to about 1.5;
An N-alkyl-meta-fluoroformanilide such as N-methyl-meta-fluoroformanilide is obtained. This reaction generally involves mixing the reactants and
This is achieved by heating to a high temperature of 200°C or higher, followed by distillation. The resulting anilide product is then hydrolyzed with an acid such as hydrochloric acid to produce N-alkyl-meta-fluoroaniline, specifically for example N-methyl-meta-fluoroaniline. A benzyl halide derivative, such as benzyl chloride, is then reacted with the formed aniline product in an approximately 1:1 molar ratio. This reaction is carried out by mixing these reactants and heating the mixture to a temperature generally between 100 DEG and 110 DEG C. to allow the reaction to proceed. Thus, aniline derivatives such as N-alkyl-N
-benzyl-meta-fluoroaniline, preferably N-methyl-N-benzyl-meta-fluoroaniline is obtained. This is then reacted with the squaric acid described herein to form the novel fluorosquaraine of the present invention, represented by the formula.

Representative examples of fluoroaniline derivatives selected to prepare the novel squaraine of the present invention include meta-fluoro-N-methyl-N-benzylaniline, meta-fluoro-N-methyl-N-para-fluoro -benzylaniline, meta-fluoro-N-methyl-N-para-chlorobenzylaniline and meta-fluoro-N-methyl-meta-
Chlorobenzylaniline is mentioned. If meta-fluoro-N-methyl-N-benzylaniline is chosen as one of the reactants, bis(2-fluoro-4-methylbenzylaminophenyl)squaraine of the formula is obtained. Similarly, meta-fluoro-N-methyl-N-para-chlorobenzylaniline, meta-fluoro-N
-Methyl-N-para-fluorobenzylaniline or meta-fluoro-N-methyl-N-meta-
If chlorobenzylaniline is chosen, squaraine compounds represented by the formulas and, respectively, shown herein are obtained.

Representative examples of aliphatic alcohols selected to prepare the fluorobenzyl squaraine of the present invention include 1-butanol, 1-pentanol, hexanol, and heptanol. Typical examples of azeotropic solvents include aromatic compounds such as benzene, toluene, and xylene.

According to one embodiment, the improved laminated photoresponsive device of the present invention comprises a support, a hole transporting layer, and a photoconductive layer disposed between the support and the hole transporting layer. It is composed of the novel fluorinated squaraine compound of the invention. In another embodiment, a laminated photoconductive layer comprising a photoconductive layer comprising the novel fluorinated squaraine compound of the present invention, and a hole transporting layer disposed between the support and the photoconductive layer. A response device is provided. The present invention also provides an improved response device useful in a printing device comprising a layer of a photoconductive composition disposed between a photogenerating layer and a hole transporting layer; An improved photoresponsive device is provided, wherein a photoconductive composition is disposed between a photogenerating layer and a support of the device, the photoconductive composition comprising the novel fluorinated squaraine compounds of the present invention. be done. For example, in the latter devices the photoconductive layer acts to enhance or reduce the inherent properties of the photogenerating layer in the infrared and/or visible region of the spectrum.

In one specific embodiment, the improved photoresponsive device of the present invention comprises one support, two hole blocking layers,
3. An optional adhesive interface layer, 4. an inorganic photogenerator layer, 5. a photoconductive composition layer containing the novel squaraine compound described herein, and 6. a hole transport layer stacked in this order. I'm taking it. Thus, in one important embodiment of the present invention, a photoresponsive device comprises an electrically conductive support, a hole-blocking metal oxide layer in contact therewith, an adhesive layer, an inorganic overcoat over the adhesive layer. a photogenerating material, e.g. a photoconductive fluorosquaraine compound of the formula capable of increasing or reducing the intrinsic properties of the photogenerating layer in the infrared and/or visible region of the spectrum, and a top layer; It consists of a hole transport layer containing a certain type of diamine dispersed in a resin matrix. When the compound of the photoconductive layer is in contact with the hole transport layer, the photogenerating layer can transport generated holes. Furthermore, the photoconductive layer does not substantially trap holes generated in the photogenerating layer. The photoconductive squaraine compound layer also acts as a selective filter, allowing certain wavelengths of light to pass through the photogenerating layer.

Another important embodiment of the present invention provides improved photoresponse as previously described, except that a photoconductive fluorosquaraine compound is disposed between the photogenerating layer and the support. directed towards the device. Thus, in this embodiment, the photoresponsive device of the present invention comprises 1 a support, 2 a hole blocking layer, 3 an optional adhesive interfacial layer, 4 a photoconductive composition comprising the novel squaraine compounds disclosed herein, 5 The inorganic photo-generating layer and the 6-hole transport layer are laminated in this order.

Exposure and erasure of the photoluminescent response device of the present invention can be performed from the front, rear, or both.

The improved photoresponsive device of the present invention can be manufactured by a number of known methods. The various parameters of the process and the order of layer application are determined according to the desired equipment. Thus, for example, a three-layer photoresponsive device can be produced by applying a photoconductive layer onto a support by vacuum sublimation and then a hole transporting layer by solution coating. According to another alternative process, a laminated photoresponsive device is prepared by providing a conductive support including a hole blocking layer and an optional adhesive layer, onto which a photogenerating layer is applied by solvent coating, laminating, or other methods. , photoconductive compositions comprising the novel squaraine compounds of the present invention such that they can increase or reduce the inherent properties of the photogenerating layer in the infrared and/or visible region of the spectrum, and hole transporting layers. It can be manufactured by using

According to one specific manufacturing sequence, a 20% transmission aluminum coated mylar support having a thickness of about 3 mils (0.0762 mm) is provided.
This is then applied with an adhesive such as 49000 available from El Dupont in a methylene chloride/trichloroethane solvent with a 1/2 mil (0.0127 mm) Bird applicator at about room temperature, followed by 100
Dry at ℃. A photoconductive layer containing the fluorinated squaraine of the present invention is then applied to this adhesive layer.
This application is also done using a Bird applicator.
Anneal at 135°C and then apply a transport layer of amine. The amine transport layer was applied by known solution coating techniques using a 5 mil (0.127 mm) Bird applicator and annealed at 135°C. This solution contains about 20% to about 80% amine carrier and about 80% to about 80% by weight
Contains a resin binder material such as 20% by weight polycarbonate material.

The improved photoresponsive device of the present invention can be incorporated into a variety of imaging devices, such as those commonly known as electrophotographic imaging processes. The improved photoresponsive devices of the present invention, further comprising an inorganic photogenerating layer and a photoconductive layer comprising the novel squaraine of the present invention, function in imaging and printing devices using visible and/or infrared light. can do. In this embodiment, the improved photoresponsive device of the present invention is negatively charged and exposed sequentially or simultaneously to light of wavelengths from about 400 to about 1000 nanometers, and the resulting image is developed and transferred to paper. . The above sequence can be repeated any number of times.

In order to better understand the invention and its features, various preferred embodiments are described in detail below.

Preferred embodiments are described below with reference to specific photoresponsive devices comprising the novel fluorobenzyl squaraine compounds exemplified herein. It is noted that equivalent compounds are also included within the scope of this invention.

FIG. 1 illustrates a photoresponsive device of the present invention, which comprises a support 1 and optionally a novel squaraine compound, bis(2-fluoro-4), dispersed in a resin binder composition 4. -methylbenzylaminophenyl) squaraine and a charge carrier hole transport layer 5 dispersed in an inert binder composition 7.

FIG. 2 shows substantially the same apparatus as that shown in FIG. However, in FIG. 2, a hole transport layer is disposed between the support and the photoconductive layer. Regarding this drawing, to be more specific,
The photoresponsive device includes a support 15, a hole transporting layer 17 comprising a hole transporting composition dispersed in an inert resin binder composition 18, and optionally a hole transporting layer 17 dispersed in a resin binder composition 21. The photoconductive layer 20 is composed of the squaraine compound of the present invention, bis(2-fluoro-4-methylbenzylaminophenyl)squaraine.

FIG. 3 shows a photoresponsive device of the present invention. The device comprises a support 8 and a hole-blocking metal oxide layer 9.
, an optional adhesive layer 10, a charge carrier inorganic photogenerating layer 11, and a bis(2- A layer 12 of an organic photoconductive composition comprising fluoro-4-methylbenzylaminophenyl (fluoro-4-methylbenzylaminophenyl) squaraine and a charge carrier or hole transport layer 14. Photogenerating layer 11 generally comprises a photogenerating material optionally dispersed in a resin binder composition 16, and similarly organic photoconductive layer 12 optionally comprises a fluorosquaraine compound dispersed in a resin binder 19. Contains. Charge transport layer 14
includes an electrified transport material such as an amine composition optionally dispersed in an inert resin binder material 23.

FIG. 4 shows essentially the same apparatus as shown in FIG. However, in the device of FIG. 4, photoconductive layer 12 is located between inorganic photogenerating layer 11 and support 8. In FIG. More specifically, in this embodiment, photoconductive layer 12 is disposed between optional adhesive layer 10 and inorganic photogenerating layer 11.

FIG. 5 shows yet another photoresponsive device of the present invention. In this device, the support 25 has a thickness of approximately
The metal oxide layer 27 is comprised of 3 mil (0.0762 mm) thick mylar including a 100 angstrom layer of 20% permeable aluminum, the metal oxide layer 27 is comprised of approximately 20 angstroms thick aluminum oxide, and the polyester adhesive layer 29 is The polyester is commercially available from El Dupont as 49000 polyester, this layer is 0.5 microns thick, the inorganic photogenerating layer 31 is approximately 2.0 microns thick, and the Na ₂ in a polyvinyl carbazole binder 32 (90% by weight) Composed of trigonal selenium (10% by weight) doped with SeO ₃ and Ne ₂ CO ₃ , the photoconductive layer 33 has a thickness of approximately 0.5 microns and is coated with a resin binder 34 (commercially available from Gutdeyer Chemical). The hole transport layer 25 is composed of 30% by weight of bis(2-fluoro-4-methylbenzylaminophenyl)squaraine dispersed in 70% by weight of PE-200 (polyester), and the hole transport layer 25 is about
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,
Contains 50% by weight of 1'-biphenyl]-4,4'-diamine.

With reference to FIGS. 1-5, the photoconductive layer can include a squaraine compound specified by the formulas.

Further, these drawings will be explained. The support is a layer of insulating material such as an inorganic or organic polymeric material, including the commercially available polymer Mylar; a layer of organic or inorganic material with or on top of a semiconducting surface layer such as indium tin oxide. It can be comprised of aluminum or layers of conductive material such as aluminum, chrome, nickel, or brass. The support may be flexible or rigid, and often takes the form of a number of different shapes, such as plates, cylindrical drums, scrolls, endless flexible belts, and the like. Preferably the support is in the form of an endless flexible belt. In some cases it is desirable to provide a coating on the back side of the support, particularly when the support is an organic polymeric material, an anti-curl layer, such as a polycarbonate material sold as Macrolon.

The thickness of the support layer is determined by many factors, including economic considerations. Therefore, as long as this layer does not adversely affect the device, e.g.
It can be sufficiently thick to exceed 100 mils (2.54 mm), or it can be a minimum thickness. In one preferred embodiment, this layer is approximately 3 mils (0.0762 mm) thick.
~10 mils (0.254mm).

The hole-blocking metal oxide layer can be comprised of a variety of suitable known materials, including aluminum oxide and the like. The main purpose of this layer is to block holes.
That is, to prevent hole injection from the support during and after charging. Typically the thickness of this layer is less than 50 angstroms.

Adhesive layers are generally comprised of polymeric materials including polyester, polyvinyl butyral, polyvinylpyrrolidone, and the like. Typically the thickness of this layer is less than about 0.6 microns.

The inorganic photogenerating layer can be comprised of known photoconductive charge carrier generating materials that are sensitive to visible light. For example, amorphous selenium, amorphous selenium alloys, halogen-doped amorphous selenium, halogen-doped amorphous selenium alloys, trigonal selenium, mixtures of periodic group A and group A elements, trigonal selenium Selenite and carbonate with selenium (these are described in U.S. Patent No.
See No. 4232102 and No. 4233283. )
These include cadmium sulfide, cadmium selenide, cadmium telluride, cadmium sulfur selenide, cadmium sulfur telluride, cadmium selenium telluride, cadmium sulfide doped with copper and chlorine, cadmium selenide and cadmium sulfur selenide. Examples of selenium alloys included in the scope of the present invention include selenium tellurium alloy, selenium arsenic alloy,
Alloys containing selenite arsenide gold and preferably halogen materials such as chlorine in amounts of about 50 to about 200 ppm are included.

The photogenerating layer can also include organic materials including, for example, metal phthalocyanines, metal-free phthalocyanines, vanadyl phthalocyanines, and the like. Examples of phthalocyanine materials are shown in U.S. Patent No.
Please refer to No. 4265990. Preferred organic materials for the photogenerating layer include vanadyl phthalocyanine and X-metal free phthalocyanine.

The thickness of this layer is typically about 0.05 microns to about 10
microns or more, preferably about
The thickness of this layer is from 0.4 microns to about 3 microns, but depends primarily on the weight of the photoconductive material, which can vary from 5 to 100% by weight.
Generally, the thickness of this layer is about 90% of the incident light directed to this layer in an image or print exposure process.
% or more is desirable. The maximum thickness of this layer is determined primarily by mechanical factors, such as whether a flexible photoresponsive device is desired.

The critical layers of the photoresponsive device of the present invention are of the formula:
This is a photoconductive layer composed of a novel squaraine compound represented by , and. These compounds are generally electronically compatible with the charge carrier transport layer and are capable of injecting photo-excited charge carriers into the transport layer, and are also compatible with the photoconductive layer and charge transport layer. Charge carriers can be transported in both directions across the interface between the layers.

Generally, the thickness of the photoconductive layer is the thickness of the other layers,
and the concentration of photoconductive material contained in this layer. Thus, this layer ranges from about 0.05 microns to about 10 microns when the photoconductive squaraine compound is present in an amount of about 5% to about 100% by weight, and preferably the thickness of this layer is about 100% by weight. It ranges from about 0.25 microns to about 1 micron when the line compound is present at about 30% by weight in this layer. The maximum thickness of this layer is determined primarily by mechanical considerations, such as whether a flexible photoresponsive device is desired.

Inorganic photogenerating or photoconductive materials can constitute 100% of each layer. Alternatively, these materials can be dispersed in a variety of suitable inorganic or resinous polymeric binder materials in amounts from about 5% to about 95% by weight, preferably from about 25% to about 75% by weight. Examples of polymeric binder resin materials that may be selected for photogenerating compositions include, for example, those described in US Pat. No. 3,121,006. This patent discloses polyesters, polyvinylbratyral, Formvar®, polycarbonate resins, polyvinylcarbazole, epoxy resins, phenoxy resins, especially commercially available poly(hydroxyether) resins. The resin binder for the fluorosquaraine photoconductive compound can be selected from the same binder materials described herein in connection with the photogenerating binder, although the resin binder for the photoconductive material is commonly marketed as Macrolon. polyesters such as those commercially available as PE-200 from Gutdeyer Chemical, polyvinyl formals and polyvinyl butyrals.

In one embodiment of the invention, a charge carrier transporting material, such as a diamine as described below, is present in the photogenerating layer or photoconductive layer, e.g., from about 0% to 60% by weight.
introduced in amounts ranging from .

Charge carrier transport layers, such as layer 14, can be comprised of any number of suitable materials capable of transporting holes. This layer generally ranges from about 5 microns to about
It has a thickness of 50 microns, preferably in the range of about 10 microns to about 40 microns. In a preferred embodiment, the transport layer comprises molecules of the formula: ##STR1## dispersed in a highly insulating transparent organic resin binder.

In the above formula, X is selected from the group consisting of ortho- _CH3 , meta- _CH3 , para- _CH3 , ortho-Cl, meta-Cl, and para-Cl. Highly insulating resins are materials that have a resistivity of at least 10 ¹² ohm-cm to prevent inadequate dark decay and are not necessarily capable of supporting hole injection. However, for insulating resins, it is about 10 to 75% by weight.
The substituted N, N, N′, corresponding to the above formula of
N'-tetraphenyl-[1,1-biphenyl]-
When it contains 4,4'-diamine, it becomes electrically active.

Compounds corresponding to the above formula are, for example, N,N'-diphenyl-N,N'-bis(alkylphenyl)-
[1,1-biphenyl]4,4'-diamine,
Alkyl is selected from the group consisting of methyl such as 2-methyl, 3-methyl and 4-methyl, ethyl, propyl, butyl, hexyl and the like. When carrying a halo substituent, the amine is N,
N'-diphenyl-N,N'-bis(halophenyl)
-[1,1'-biphenyl]-4,4'-diamine, and halo is 2-chloro, 3-chloro or 4-chloro.

It is possible to form a layer that transports holes by dispersing it in an electrically inert resin. Other electroactive small molecules include bis(4-diethylamino-2-methylphenyl)phenylmethane; 4',4'-bis(diethylamino)-2',2'-dimethyltriphenylmethane; bis-4- (diethylaminophenyl)phenylmethane; and 4,
4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane is mentioned.

Other charge carrier transport molecules may be selected for the photoconductive device of the present invention provided that the objectives of the present invention are achieved.

Examples of highly insulating transparent resin materials or inert binder resin materials for the transport layer include materials such as those described in US Pat. No. 3,121,006; see that patent. Specific examples of organic resin materials include polycarbonate,
Acrylate polymer, vinyl polymer, cellulose polymer, polyester, polysiloxane,
Mention may be made of polyamides, polyurethanes and epoxies as well as block, random or alternating copolymers thereof. Preferred electrically inert binder materials have a molecular weight of about
20000 to about 100000 polycarbonate resin,
Particularly preferred are those having a molecular weight in the range of about 50,000 to about 100,000. Generally, the resin binder will contain from about 10% to about 75% by weight of the active material corresponding to the above formula, preferably from about 35% to about 50% of this material.

Also within the scope of the present invention are methods of forming images using the photoresponsive devices described herein. These imaging methods generally involve forming an electrostatic latent image on an imaging element, developing this latent image with a known developer composition, and then transferring the image to a suitable support. It includes the step of permanently fixing this image. In environments where this device is used in print mode, the imaging method includes similar steps, but the exposure step is accomplished by a laser device or image bar rather than a broad spectrum white light source. They differ in some respects. In the latter embodiment, a photoresponsive device sensitive to infrared light is chosen.

The invention will now be described in detail with reference to certain preferred embodiments of the invention. It should be understood that these embodiments are for illustrative purposes only. The invention is not limited to the materials, conditions or process parameters recited herein. All parts and percentages are by weight unless otherwise specified.

Example: 124.7 g (1.12 mol) of m-fluoroaniline manufactured by Aldrich Chemical in a 500 ml round bottom flask.
and 178.6 g (1.68 mol) of trimethyl orthoformate manufactured by Aldrich Chemical were added. Next, concentrated sulfuric acid 4.6
g was added with mixing. The flask was then attached to a Vigreux distillation column (3/4 inch (1.9 cm) diameter x 12 inches (30 cm) long) with a vacuum jacket.
The mixture was heated with stirring at an oil bath temperature of approximately 120°C. Approximately 175 ml of methanol was distilled in 1 hour. The bath temperature was then slowly raised to about 205°C and held at that temperature for 30 minutes. An additional approximately 25 ml of volatile material was distilled during this time.

The reaction mixture was then cooled to room temperature and the distillation apparatus was connected to a vacuum pump. The separated clear yellow liquid product, N-methyl-m-fluoroformanilide, was isolated and purified by vacuum distillation to yield 108.4 g (approximately 63% yield) of this compound. This product boils at about 78°C at 0.19 mmHg.

In the flask of Example 1, 108.4 g of N-methyl-m-fluoroformanilide (0.71
mol) was hydrolyzed with 350 ml of 10% hydrochloric acid for 2 hours at reflux temperature. The mixture was then cooled to room temperature and 15
% potassium hydroxide solution. The resulting organic layer was then separated. The resulting aqueous layer was first saturated with potassium carbonate and then extracted with ether (2x400ml). The organic fractions were combined, washed with water, and dried over anhydrous magnesium sulfate. After removing the ether using a rotary evaporator, vacuum distillation was performed to obtain N-methyl-m-fluoroaniline.
76.5 g (87% yield) was isolated as a colorless liquid.
This product boils at about 80°C at 10mmHg.

MS: Mass spectrum 125 (M ⁺ ) Calculated value (as C ₇ H ₈ NF) C, 67.18, H, 6.44, N, 11.19, F, 15.18 Measured value C, 67.24, H, 6.43, N, 11.32, F, 14.92 Example A mixture of the N-methyl-m-fluoroaniline prepared in the example, 18.3 g of benzyl chloride (0.14 mol, manufactured by Aldrich Chemical), 11.9 g of anhydrous sodium acetate and 0.12 g of iodine was added to about
Heated at an oil bath temperature of 110°C for 12-16 hours. The reaction mixture was then cooled to room temperature and about 100 ml of water was added.
Transferred to a 250 ml separatory funnel. The product solution was made basic with sodium hydroxide solution and then extracted with ether (4x80ml). The combined ether extracts were washed with water and then dried over anhydrous magnesium sulfate. After removing the ether on a rotary evaporator, the product was isolated by vacuum distillation using a Vigreux distillation column with a vacuum jacket. The product N-methyl-N-benzyl-m-fluoroaniline is a colorless liquid at approximately 0.2 mmHg.
isolated at 133-138°C. Yield 21.8g
(about 90%).

MS: 215 (M ⁺ ) Calculated value (C ₁₄ H ₁₄ NF): C, 78.11, H, 6.56, N, 6.51, F, 8.83 Measured value C, 78.14, H, 6.72, N, 6.54, F, 8.76 Implemented Example Following the procedure described in the example, 17.5 g (0.14
mol) of N-methyl-m-fluoroaniline,
N-Methyl-N- from 23.7 g (0.14 mol) p-chlorobenzyl chloride (Aldrich), 11.9 g anhydrous sodium acetate and 0.12 g iodine
p-Chlorobenzyl-m-fluoroaniline was prepared. Yield 25.8 g (74%) 162-170°C at boiling point 0.13 mmHg, MS: 249 (M ⁺ ) calculated value (C ₁₄ H ₁₃ NFCl) as C, 67.34, H, 5.25; N, 5.61; F, 7.61; Cl, 14.20 Measured value C, 67.45; H, 5.22; N, 5.58; F, 7.47; Cl, 14.31 Example 26.3 g (0.21 mol) N-methyl-m-fluoroaniline, 30.6 g (0.21 mol) p N-Methyl-Np-fluorobenzyl-m-fluoroaniline was prepared from -fluorobenzyl chloride (Aldrich), 17.8 g anhydrous sodium acetate and 0.18 g iodine according to the procedure of the example. Yield 35.4g (72%) Boiling point 131-137℃/0.2mm
Hg.

MS: 233 (M ⁺ ) Calculated value (as C ₁₄ H ₁₃ NF ₂ ) C, 72.09; H, 5.62; N, 6.00; F,
16.29 Measured value C, 72.00; H, 5.64; N, 5.92; F, 16.14 Example According to the procedure described in the example, 17.5 g (0.14
mol) of N-methyl-m-fluoroaniline, 23
N-methyl-N-m-chlorobenzyl-m-fluoroaniline was prepared from m-chlorobenzyl chloride (Aldrich), 11.9 g of anhydrous sodium acetate and 0.12 g of iodine. Yield 28.6g (83.7%) Boiling point 172°C/0.07mmHg.

MS: 249 (M ⁺ ) Calculated value (as C ₁₄ H ₁₃ NFCl) C, 67.34, H, 5.25; N, 5.61; Cl, 14.20 Measured value C, 67.20, H, 5.39, N, 5.77, Cl, 14.42 Implemented Example: 1.14 g (10 mmol) of squaric acid and 4.31 g (20 mmol) of N-methyl-N-benzyl-m-fluoroaniline, prepared according to the procedure in the example, were mixed with toluene (40 ml) in an oil bath temperature of about 130°C. ) and 1-butanol (40ml) at reflux. Water was azeotropically removed using a direct trap. After 8 hours, the reaction mixture was cooled to room temperature. The product, bis(2-fluoro-4-methylbenzylaminophenyl)squaraine, was collected by filtration. The product was washed with ether and dried in vacuo to yield 0.26 g (4.7%) of green dye product.

Melting point 239.5-240.5℃ Calculated value: (as C ₃₂ H ₂₆ N ₂ F ₂ O ₂ ) C, 75.58, H, 5.15, N, 5.51, F, 7.47 Measured value C, 75.43, H, 5.10, N, 5.68, F, 7.38 Example 1.14 g (10 mmol) of squaric acid and 4.31 g
(20 mmol) of N-methyl-N-benzyl-m
- Fluoroaniline under reduced pressure of about 70 mmHg, about
The reaction was carried out in 50 ml of 1-heptanol at an oil bath temperature of 105°C. Water was azeotropically distilled off and collected using a diesel tank trap. After 20 hours, the mixture was cooled to room temperature and filtered. The dye product was washed with methanol and ether and dried in vacuum to give 1.48 g.
(29.1%) green pigment bis(2-fluoro-4-
methylbenzylaminophenyl) squaraine was obtained. This product was identified according to the procedures in the example, and substantially the same results were obtained.

Example Instead of N-methyl-N-benzyl-m-fluoroaniline, 4.66 g (approximately 20 mmol) of N-methyl-N-p prepared according to the procedure of the example
- The procedure of the example was repeated except that fluorobenzylaniline was used. 0.05 g (yield 0.9%) of the dye, bis(2-fluoro-4-methyl-p-fluorobenzylaminophenyl)squaraine, was obtained.

Melting point: 201.5-202.5℃ Calculated value: (as C ₃₂ H ₂₄ N ₂ F ₄ O ₂ ) C, 70.58, H, 4.44, N, 5.14, F, 13.96 Measured value C, 70.60, H, 4.50, N, 5.03 , F, 14.17 Example The procedure of the example was repeated except that 4.66 g (20 mmol) of N-methyl-N-p-fluorobenzylaniline was used instead of N-methyl-N-benzyl-m-fluoroaniline. Ta. Product, bis(2-fluoro-4-methyl-p-fluorobenzylaminophenyl)squaraine 1.57 g (yield
28%) were obtained. This product was identified following the procedure of Example 9 with virtually identical results.

Example XI The procedure of the example was repeated except that 4.98 g (20 mmol) of N-methyl-N-p-chlorobenzyl-m-fluoroaniline was used instead of N-methyl-N-benzyl-m-fluoroaniline. repeated. Bis(2-fluoro-4-methyl-p-chlorobenzylaminophenyl)squaraine 1.64 g (yield
28.4%) was obtained.

Melting point: 245.5-247.0℃ Calculated value: (as C ₃₂ H ₂₄ N ₂ O ₂ F ₂ Cl ₂ ) C, 66.56, H, 4.19, N, 4.85, F, 6.58, Cl, 12.28 Measured value C, 66.50, H , 4.33, N, 4.76, F, 6.54, Cl, 12.27 Example The procedure of the example was repeated except that m-fluoroaniline was used. Bis(2-fluoro-4-methyl--m-chlorobenzylaminophenyl)squaraine 0.67 g (yield
11.6%) was obtained.

Melting point: 220.6-221.6℃ Calculated value: (as C ₃₂ H ₂₄ N ₂ O ₂ F ₂ Cl ₂ ) C, 66.56, H, 4.19, N, 4.85, F, 6.58, Cl, 12.28 Measured value C, 66.67, H , 4.30, N, 4.86, F, 6.72, Cl, 12.28 Example was manufactured. Specifically, we prepared a grained aluminum support with a ball of 150 microns in thickness, and applied it to PCR Research Chemicals (Florida) using a multiple clearance film applicator.
A layer of a commercially available ethanolic solution of N-methyl-3-aminopropyltrimethoxylane (1:2 volume ratio) with a wet thickness of 0.5 mil (0.0127 mm)
A photoresponsive device was created by coating with The layer was then dried at room temperature for 5 minutes and further cured in a forced draft oven at 110°C for 10 minutes.

Next, a photoconductive layer containing 30% by weight of bis(2-fluoro-4-methylbenzylaminophenyl)squaraine was prepared as follows.

Separate 2oz (60ml) amber pins,
0.33g of the above squaraine, 0.75g of Vitel PE
-200® (polyester from Gutdeyer), 85 g 1/8 inch (3.2 mm) stainless steel shot and 20 ml of methylene chloride were added. The above mixture was ball milled for 24 hours. The resulting slurry was then applied to an aluminum support at a wet thickness of 1 mil (0.0254 mm) using a multiple clearance film applicator. This layer was then air dried for 5 minutes. The resulting device was then dried in a forced draft oven at 135°C for 6 minutes.
The dry thickness of the squaraine layer was approximately 1 micron. A charge transport layer was overcoated on top of the photoconductive layer. This charge transport layer was prepared as follows.

A transport layer consisting of 50% by weight of Macrolon (registered trademark) (a polycarbonate resin sold by Ralben Sabritken Bayer AG) was mixed with 50% by weight of N,
Mixed with N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine. This solution was mixed at 9% by weight in methylene chloride. All these ingredients were placed in an amber bottle and dissolved. The mixture was applied to the surface of the squarine photoconductive layer using a multiple clearance film applicator (15 mil (0.38 mm) wet gap thickness) to form a layer with a dry thickness of 30 microns. The device was then air dried at room temperature for 20 minutes and further dried in a forced draft oven at 135°C for 6 minutes.

The photoreceptor device was then incorporated into an electrophotographic image testing device and developed with toner particles containing styrene n-butyl methacrylate resin to obtain high quality copies with excellent resolution.

EXAMPLE A 3 mil (0.0762 mm) thick aluminum coated Mylar support was prepared and treated with methylene chloride and 1,1,2-trichloroethane (4:
Apply a layer of DuPont 49000 adhesive (DuPont polyester) at 0.5% by weight (by volume) to a wet thickness of 0.5 mil (0.0127 mm) using a Bird applicator.
It was applied so that This layer was dried for 1 minute at room temperature and then for 10 minutes at 100° C. in a forced draft oven. The dry thickness of the resulting layer was 0.5 micron.

10% by weight trigonal selenium, 25% by weight N,
A photogenerator layer containing N'-diphenyl-N,N'-bis(3-methylphenyl)1,1'-biphenyl-4,4'-diamine and 65% by weight polyvinylcarbazole was prepared as follows.

A 2 oz (60 ml) amber pin was charged with 0.8 g of polyvinylcarbazole and 14 ml of a 1:1 volume ratio of tetrahydrofuran/toluene. 3.8 g of trigonal selenium and 100 g of 1/8 inch (3.2 mm) stainless steel shot were then added to this solution.
This mixture was then placed on a ball mill for 72-96 hours. Next, 5 g of the resulting slurry was dissolved in 6.3 ml of tetrahydrofuran to toluene (1:1 by volume) with 0.18 g of polyvinylcarbazole and 0.15 g.
was added to a solution of N,N'-diphenyl-N,N'-bis(3-methylphenyl)1,1'-biphenyl-4,4'-diamine. This slurry was then placed on a sheaker for 10 minutes. The resulting slurry was then applied to the polyester interface using a bird applicator to a wet thickness of 0.5 mil (0.00127 mm) and the resulting layer was placed in a forced draft oven.
It was dried at 135° C. for 6 minutes to obtain a layer with a dry thickness of 2.0 microns. A photoconductive layer containing 30% by weight of bis(2-fluoro-4-methylbenzylaminophenyl)squaraine was prepared by repeating the procedure of the example. This layer was applied onto the photogenerator layer using a bird applicator to a dry thickness of 1 micron.

The photoconductive layer was then overcoated with a charge transport layer prepared as follows.

A transport layer consisting of 50% by weight of Macrolon (registered trademark) (polycarbonate resin sold by Ralben Sabritken Bayer AG) was mixed with 50% by weight of N,N'-
Mixed with bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine. This solution was mixed with methylene chloride to give a concentration of 9% by weight. All of these ingredients were dissolved in an amber pin. The resulting mixture was then applied to the surface of the photoconductive squaraine layer to obtain a layer with a dry thickness of 30 microns. The application was done with a multiple clearance film applicator (15 mil wet gap thickness). The resulting device was then air-dried at room temperature for 20 minutes, then in a forced draft oven at 135 °C for 6
Dry for a minute. An aluminum-coated mylar support, a photogenerating layer of trigonal selenium, and a bis(2)
A photoresponsive device was obtained comprising a photoconductive layer of -fluoro-4-methylbenzylaminophenyl) squaraine and, as top layer, a charge transport layer of the above-mentioned amine.

Repeat the example and the procedure of the example except that a selenium-tellurium alloy containing 75% by weight selenium and 25% by weight tellurium or an arsenic-selenium alloy containing 99.99% by weight selenium and 0.1% by weight arsenic is selected as the photogenerating layer. Other photoresponsive devices can also be created thereby.

Further, as squaraine photoconductive compositions, bis(2-fluoro-4-methyl-p-chlorobenzylaminophenyl)squaraine, bis(2-fluoro-4-methyl-p-fluorobenzylaminophenyl)squaraine A photoresponsive device was prepared by repeating the operations in Example and above, except that 1 and bis(2-fluoro-4-methyl-m-chlorobenzylaminophenyl)squaraine were selected.

The devices prepared in Examples and 2 were tested for photosensitivity in the visible and infrared region of the spectrum. This test was conducted by negatively charging the devices to -800 volts by corona discharge and then simultaneously exposing each device to monochromatic light in the wavelength range from about 400 to about 1000 nanometers. The photoresponsive device of the example was shown to be responsive to light in the wavelength range of 400-950 nanometers and sensitive to visible and infrared light. The example device showed excellent responsiveness to light in the wavelength range of about 400 to about 950 nanometers, indicating that the device is sensitive to visible and infrared light.

Furthermore, the photoresponsive device produced according to the example was incorporated into an electrophotographic image testing device, and the styrene n-
Developed with toner particles containing butyl methacrylate resin to obtain high quality copies with excellent resolution.

Although the present invention has been described with reference to particular preferred embodiments, it is not intended that the invention be limited thereto; on the contrary, those skilled in the art will recognize that various modifications and changes will occur. Dew.
Such modifications and changes are within the spirit of the invention and are intended to be included within the scope of the following claims.

[Brief explanation of the drawing]

1 to 5 are partially schematic cross-sectional views of the photoresponsive device of the present invention. DESCRIPTION OF SYMBOLS 1...Support, 3...Photoconductive layer, 4...Resin binder composition, 5...Hole transport layer, 7...Resin binder composition.

Claims (1)

[Scope of Claims] 1. Support, and bis(2-fluoro-4-methylbenzylaminophenyl)squaraine (general formula) General formula Bis(2-fluoro-4-methyl-p-chlorobenzylaminophenyl)squaraine (general formula) General formula Bis(2-fluoro-4-methyl-p-fluorobenzylaminophenyl)squaraine (general formula) General formula and Bis(2-fluoro-4-methyl-m-chlorobenzylaminophenyl)squaraine (general formula) General formula A photoresponsive imaging member comprising a photoconductive layer comprising a squaraine selected from the group consisting of: and a diamine hole transporting layer.